Karl krekelee and eduard martz



UNITED STATES PATENT @rricn.

KARL KREKELER AND EDUARD MARTZ, OF ELBERFELD, GERMANY, ASSIGNQRS TO THEFARBENFABRIKEN OF ELBERFELD COMPANY,

OF NEW YORK, N. Y.

BROWN TRISAZO DYE.

SPECIFICATION formingpart of Letters Patent No. 602,858, dated April 26,1898.

Application filed November 23, 1897. Serial No. 659,582. (Specimens)Patented in Germany September 15,1891, No. 65,262; in England December28, 1891,1111. 22,641; in France A ril 28,1892,N0. 221,233; in ItalyJune 30,1892,XXVL 32,191, and LXIII, 186, and in hustria Hungary October3,1892, No. 1,2 12 and No. 16,870.

No. 32,191, Reg. Att., v01. LXIII,N0.186,-

dated June 30, 1892, and in Austria-Hungary, No. 1,242 and No. 16,870,dated October 3, 1892;) and we hereby declare the following to be aclear and exact description of our invention.

Our invention relates to the production of a new class of trisazodyestuffs by diazotizing tetrazo bodies of the general formula in whichformula P represents a radical of the benzidin series, such as diphenyl,ditolyl, diphenyl ether, or the like; R, the radical of anorthooxycarbonic acid of the benzene series, such as salicylic acid orcresotinic acid; 0, the radical of the so-called Clevesalphanaphthylamin-beta-sulfonic acid (1.6 or 1. 7)

and combining the diazo body thus obtained with one molecule of anorthooxycarbonic acid, such as salicylic acid or cresotinic acid. Thedyestuffs thus obtained have the general formula (P, R, and 0 meaning inthis formula the above-defined radicals.) They represent dark powderswhich dissolve in water with a color varying from yellowish brown tobrown and dye cotton from yellowish-brown to brown shades, which, by atreatment with a solution of bichromate of soda or of an analogouschromium salt, with or without the presence of copper salts, become morereddish brown and faster to washing and against the action of light. Thenew coloring-matters are also capable of dyeing wool in acid-baths. Theshades thus obtained are similar to those produced on cotton.

In carrying out our new process practically we can proceed as follows:18.4 kilos, by weight, of benzidin are diazotized in the usual manner bymeans of fourteen kilos, by weight, of sodium nitrite. To the icy-colddiazo solution an icy-cold solution of fourteen kilos, by weight, ofsalicylic acid and seventy kilos, by weight, of sodium carbonate (Na OOin four hundred liters of water is added with stirring. hen theformation of the intermediate product is finished, a cold solutionprepared by dissolving 2&5 kilos, by weight, of the sodium salt ofalpha-naphthylaminbeta-monosulfo-acid (1.6) in three hundred liters ofwater is added. After about athree hours stirring the formation of theintermediate dyestuff is complete. The mixture is subsequentlyacidulated by means of hydrochloric acid and filtered. The dyestuff acidthus obtained is dissolved in fifteen hundred liters of a 2. 5-per-cent.soda-lye, then quickly mixed with a solution of eight kilos, by weight,of sodium nitrite, flVG hundred kilos, by weight, of ice, and onehundred and fifty kilos, by weight, of hydrochloric acid, (20 Baum.)This mixture is stirred for about twelve hours, and then the resultinginsoluble diazo compound is filtered and pressed. Subsequently it ismixed with ice and water to a thin paste, which is slowly stirred intoan icy-cold concentrated solution of fourteen kilos, by weight, ofsalicylic acid and one hundred and forty kilos, by weight, of sodiumcarbonate. After stirring for twelve hours the mixture is heated toabout 70 eentigrade. The dyestufi thus complete is salted out in theusual manner. Then it is filtered ed,

pressed, dried, and pulverized. It is the sodium salt of an acid havingthe formula and represents a dark-brown powder, soluble in water with ayellowish-brown color and in concentrated sulfuric acid with a bluecolor. From this solution a dark-brown flaky precipitate is obtained onthe addition of a sufficient quantity of ice.

The new coloring-matter dyes unmordanted cotton yellowish-brown shades,which when treated with a solution of a chromium salt, with or withoutthe presence of salts of copper, become more reddish brown and faster towashing and against the action of light.

On unmordanted Wool the coloring-matter produces in acid -bathsyellowish brown shades, which on a treatment with chromium salts becomefast against milling.

Having now described our invention and in i what manner the same is tobe performed, what we claim as new, and desire to secure by LettersPatent, is-

1. The process for producing new trisazoi dyestuifs by combiningthe'diazo derivatives of the disazo compounds hereinbefore defined suchas the combination of one molecule of tetrazodiphenyl with one moleculeof sali cylic acid and one molecule of Cleves naphthylaminsulfo-acid,having the general for- N:N-Oleves naphthylaminsulfo-acid with onemolecule of an orthooxycarbonic acid of the benzene series substantiallyas:

hereinbefore described.

the body having the formula Sa1icy1ic aeid Benzidin (tetrazotized)Cleves naphthylaminsulfo-acid with one molecule of salicylic acidsubstan-g tially as described.

3. As new articles of manufacture the new 1' trisazo dyestuffsobtainable from the diazo derivatives of the disazo compounds, such asthe combination of one molecule of tetrazodiphenyl with one molecule ofsalicylic acid and one molecule of Oleves naphthylaminsulfo-acid, havingthe general formula:

N:NorthooXycarbonic acid P N:N- Oleves naphthylaminsulfo-acid with onemolecule of an orthooxycarbonic -acid of the benzene series, being darkpowders, soluble in water with a color varying from yellowish browntobrown, dyeing unmordanted cotton from yellowish-brown to brown shadeswhich whentreated with solutions of chromium and copper salts becomemore reddish brown and faster to washing and against the action oflight, capable of dyeing wool in acid-baths shades similar to thoseproduced on cotton substantially as described.

4. As a new article of manufacture the specific dyestufi obtainable fromthe diazo derivativeof the body, having the formula:

. Salicylic acid Benzidin (tetrazotized) Clves naphthylaminsulfo-acidwith one molecule of salicylic .acid being an alkaline salt of an acidhaving the formula Salicylic acid Benzidin (tetrazotized) Clvesnaphthylaminsulfo-acid (diazotized -salicylic acid.

representing in the form of the sodium salt a dark-brown powder, solublein water with a yellowish-brown color, in concentrated sulfuric acidwith a blue color from which solution a dark-brown flaky precipltate isobtained on the addition of a sufficient quantity of ice, dyeingunmordanted cotton yellowish-brown shades which when treated withsolutions of chromium and copper salts become more reddish brown andfaster to washing and against the action of light, yielding on wool inacid-baths yellowish-brown shades which on a treatment with chromiumsalts become fast against milling substantially as 2. lhe process forproducing a new trisazo described 7 dyestuif by combining the diazoderivative of I In testimony whereof we have signed our names in thepresence of two subscribing wit- 5 nesses.

KARL KREKELER. EDUARD MARTZ.

Witnesses:

R. E. JAHN,

OTTO KoNIG.

